Process for breaking petroleum emulsions employing certain polyepoxide treated amine-modified thermoplastic phenol-aldehyde resin



United States Patent PROCESS FOR BREAKING PETROLEUM EMUL- SIONS EMPLQYING CERTAIN POLYEPOXIDE TREATED AMINE-MODIFIED THERMOPLASTIC 'PHENOL-ALDEHYDERESINS Melvin De Groote, University City, and Kwan-Thrg Siren, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware NoDrawing. Application February 24, 1953, Serial No. 338,577

20 Claims. (Cl. 252-633) The present invention is a continuation-impart of our co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned.

The present invention is concerned with dernulsification which involves the use of certain polyepoxide-- treated amine-modified thermoplastic phenol-aldehyde resins forthe resolution ofpetroleum emulsions. More specifically, the invention relates to the breaking of emulsions of the water-in-oil type characterized by subjecting theemulsion to the action of a demulsifier including products obtained by the method of first condensing certain phenol-aldehyde resins, hereinafter described in detail, with certain cyclic amidines, hereinafter described in detail, and formaldehyde, which condensation is followed by-reaction of theresin condensate with certain phenolic polyepoxides, also hereinafter described in detail, and cogenerically associated compounds formed in the preparation of the polyepoxides.

In preparing diepoxidesor the low .molal polymers one does usually obtain cogeneric materials which may include monoepoxides. However, the cogenericmixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the invention is represented by the use of the reaction product of (A) an aminemodified phenol-aldehyde resin condensate as described, and (B) a member of the class consisting of (1) compounds of the following formula the preparation of (-1)-preceding.

It so happens that-the bulk of information concerned with the preparation of compounds having two oxirane rings appears in the patent literature and for the most part in the recent patent literature. Thus, in the subsequent text there are numerous references to such patents for purpose of supplying information and also for purpose of brevity.

Notwithstandingthe fact that subequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygenatom as derived from a ketone .or aldehyde.

-E l mi 1:956

If it were not for the expense involved in preparing and purifying the monomerwe would prefer it to any other form, i. e., in preference to the polymer or mixture of polymer and monomer.

Stated another way we wouldprefer to,use materials of the ltind described, for example, in Patent No. 2,530,353, dated November 4, 1950. Saidpat ent describes compounds having the general formula wherein R is an aliphatic hydrocarbon bridge, each, n independently has one of the values 0 and 1, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far as polyepoxide goes, is as follows: i

U. S. Patent No. Dated Inventor July 5, 1939 Sehafer.

Mikeska et al.

Do. Do. Cohen et a1 Roseu et al Roseu. Britten et al. October 12 1943 Winning-ct a1. November 4, 1947. De Groote et a]. December 28, .1948 Swern et a1. February 15, 1949. Wyler. February 15, 1949 Do. September 27, 1949---. Dietzler. November 15, 1949.--. -Mikeska et a1. April 4, i950 Dietzler et 2.1. April 11, 1950... Bock ct al. May 2, 1950... Beader et al. Ju y 18, 1950 Stevens et al. July 18, 105 D0. July 18, 1950. Do. October 17, 1950 Dietzler November 14, 1950.... Havens. August 14, 1951 ,De Grooteet al. November 20, 1951..-. Newey et :11. January 8, 1952 Zecb. January 8, 1952.... Albert.

January 22, l952 Greenlee.

The compounds having two oxirane rings and v.ern-

are compounds of the following formulaand cogenerically associated compounds formed in theirpreparation: in which R represents a divalent radical. selected from the class of ketone residues formed by,the,elimination of the ketonic oxygen atom and aldehyde residuesobthe divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent disulfide radical --SS; andRrO is the divalent radical obtained by the elimination ofla hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R", and R represent a member or we class of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a whole number not greater than 3. The above mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins, Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents,

(condensate) etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with amine. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetra- V ethyleneglycol.

The express epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4- epoxybutane (1,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristics of a comparatively insoluble resin.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group. I

To illustrate the products which represent the subject matter of the present invention reference Will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and triethanolamine. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which the various characters have their previous significance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking.

-Not only does this property serve to differentiate from instances Where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% distilled water at ordi nary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylenemethanol mixture, for instance, 5% to 10% of acetone.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,2epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Groll.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of thc water-in-oil type, We particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with Water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydro- .5 philechara'cter to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al'. In said patent such t -st for emulsific'ation using a water-insoluble solvent, generally xylene, is described as an index of surface activity;

In the present instance the various condensation products as such or in the'form of free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble'solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of Water. Such test is obv-iously'the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into eight parts with Part 3, in turn, being divided into three subdivisions:

Part 1. is concerned with our preference in regard to the polepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation ofmonomeric diepoxide, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing lowmolal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part ,4 is concerned with .the phenol-aldehyde resin whichis subjected to modification by condensation reactionto yield the amine-modifiedresin;

Part 5 is concerned with appropriate basic cyclic amidineswhich may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials nad examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1.

As will be pointed out subsequently, the preparation of polyepoxides-may include the formation of a .small amount of material having more than two epoxide groups permolecule. If such compounds are formed they are perfectly suitable except vto the extent they may tend to produce ultimate reaction products which are not solvent-soluble. liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specificobjective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from "phenol (hydroxybenzene') or substituted of the monomer or separation of the monomer from the' remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be preparedwithout added expense for separation, our preference'would be to use the monomer. Certain monomers have been prepared and described in the literature and will be' referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts.- Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimumamount of higher polymers.

It has beenpointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for .most practical purposes it means instances where the phenolic nuclei are either uniteddirectly' without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide' reactants can be produced-in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bisphenol A. It can be used as such, or the monomer canbe separated by an added step which involves additional expense. This compound of the following structure is preferred'as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. it is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, What is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a loW-molal sulfur-containing compound can react with epichlorohydrin there be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. If a product such as bisphenol A is employed the ultimate compound in monomeric form employed as a reactant in the present invention has the following structure:

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

OH OH Cl Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difficulty stems from a number of sources and a few of the more important ones are as follows:

(1) The closing of the epoxy ring involves the use of caustic soda or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds:

OH OH (2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bisphenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, an'd at times apparently does, take place in connection with compounds having one, or in the present instance, two sub stituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and in, evitabiy present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the factv that in the ordinary course of reaction a diepoxide, such as may react with a mole of bisphenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspond in every respect except that one terminal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two bydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course, closely related to the actual method of preparation which is discussed in greater detail in Part 3, particularly subdivisions A and B. There can be no clear line between the theoretical aspect and actual preparative steps. However, in order to summarize or illustrate what has been said in Part 1, immediately preceding reference will be made to a typical example which already has been employed for purpose of illustration. The particular example is It is obvious that two moles of such material combine readily with one mole of bis-phenol A,

to produce the product which is one step further along, at least, towards polymerization. In other words, one prior example shows the reaction product obtained from one mole of the bisphenol A and two moles of epichlorohydrin. This product in turn would represent three moles of bisphenol A and four moles of epichlorohydrin.

For purpose of brevity, without going any further, the next formula is in essence one which, perhaps in an idealized way, establishes the composition of resinous products available under the name of Epon Resins as now sold in the open market. See, also, chemical pamphlet entitled Epon Surface-Coating Resins, Shell Chemical Corporation, New York city. The word Epon is a registered trademark of the Shell Chemical Corporation.

cm H r- CH: CH: n" OH: 0H, 5 1 Y l C I CHg For the purpose of the: instant invention n' mayfrepre p p sent a number including. ,zero, and at the; most a. low At the expense of repetition of what appeared. previnumber such as 1, 2 or 3; This limitation doesnot e'xist I ously,: it may be wellto recall thatzthese materials may in actual efforts to obtain resinsas difierentiatedirom the; vary. from simple solublenon-resinous to complex nonherein described soluble materials.- It is quite-prolzzable1v soluble-resinousepoxideswhich are'polyether derivatives that in the resinous productsas marketed forv coating.use,-.:-: of polyhydric. phenols containingan average of more than the value of n is usually substantially-higher; Note' one epoxide-group per molecule and free'from functional again what has been said previously that any formula groups other than epoxide and hydroxyl groups. The is, at best ,an over-simplificatiomor at the most represents former are here included; but thelatter, i. e., highly resperhaps;only.the;more important:orprineipalconstituent inous. orv insoluble types, are .n'ot.. V

or oonstit uen t s;.;- {These-materials.mayyary fromssimple I In summary then-in light or What-has been said,.eom-. non resinousto complex resinousepoxides-which arepolye pounds suitablefor reaction with amines maybe sumether derivatives of polyhydric phenols containing an avmarized by the following formula:

craze. of more. than oneepoxidegroupper molecule and free from functional groups other ,than epoxide and. or forzgreateresimplicity theformula could be restated Referring nowtotwhat hasebeen said previously, to Wit, in which the various characters have their prior significompounds having both an epoxy ring or the equivalent canoe and in which R10 is the divalent radical obtained and also a hydroxyl group, one need go no further than by the elimination of a hydroxyl hydrogen atom and a to consider the reaction product of 40 nuclear hydrogen atom from the phenol Q a; i H H H H H H OH 0 0H, 5 0 'lL i m and bisphenol A in a mole-for-mole ratio, .since,the initial reactant would y l a product having an unreacted p xyin which R, R", and R' represent a member of the class T1118 and reactive y y faldlcals- Referring g n consisting of hydrogen and hydrocarbon substituents of 10 a P Q formula, COHSldel' an mpl Where tWO the aromatic nucleus, said substituent member having not 1119165 of 131519951101 A have been reacted with 3. moles 'of over 18 carbon atoms; n represents an integer selected epichlorohydrin. The simplest compound formed would from the class of zero and l, and n represents a whole be thus: number not greater than 3;

(]H: (|)H3 CHs'" H, 0H, CH; 111, 011 C l I 0 o \CH:

Sucha'eompoundisicomparabl'e to other compounds hav- PART 3 ing both the hydroxyl and epoxy ring such as 9 ,10-epoxy S A octadecanol. The ease with which this type of compound u polymerizes is pointedout by U: S. PatentNo. 2,457,329, The preparations of the diepoxy derivatives of the didated December 28, 1948, to Swern et a1, phenols, which are sometimes referred to as diglycidyl The same difficulty which involves the tendency to polyethers, have been described in a number of patents. For

merize on the part of compounds havinga reactive ring convenience, reference will be made to two only, to wit,

and a hydroxyl radical may be illustrated by compounds aforementioned U. S. Patent 2,506,486, and aforemenwhere, instead of the oxirane ring (1.,2-epoxy ring) there tioned UL-S. Patent-No. 2,530,353;

is present a 1,3-epoxy ring. Such compounds are deriva- Purely by way of illustration, the following diepoxides, tives of trimethylene oxide rather than ethylene oxide. or diglycidyl ethers as they are sometimes termed, are in- -See U. S. Patents Nos. 2,462,047 and 2,462,048, both eluded for purpose of illustration. These particular comdated February 15, 1949, to Wyler; pounds are described in the two patents just mentioned.

TABLE I Ex- Patent ample Diphenol Diglycidyl ether refernumber ence Dl(epoxypropoxyphenyDmethane 2, 506, 486 Di(epoxypropoxyphenyl)methylmethane. 6, 486 D1(epoxypropoxyphenyl)dimethy1methane- 2, 506, 486 Di(epoxypropoxyphenyl)ethylmethylmethane. 2, 506, 486 Di(epoxypr0poxyphenyl)diethylmethane 2, 506, 486 Di(epoxypropoxyphonyl)methylpropylmethane- 2, 506, 486 Di(cpoxypropoxyphenyl)methylphenylmethane. 2, 506, 486 D i(epoxypropoxyphenylg ethylphenylmethane 2, 506, 486 Di(ep0xypr0poxyphenyl propylphen lmethane 2, 506,486 D1(epoxypropoxyphenyl)butylpheny ethane 2, 506, 486 (CH3C5H4)CH(C H4OH)2 Di(ep0xypropoxyphenyl)tolylmethane 2, 506,486 (CHaCaHO 0 (CH3) (CaH4OH) Di(epoxypropoxyphenyl) tolylmethylmethane 2, 506, 486 Dihydroxy diphenyl 4,4-bis(2,3-epoxypropoxy)diphenyl 2, 630, 353 (OH3)O(C4H5.CQH3OH)2 2,2-bis(4-(2,3-epoxypropoxy)2-tertiarybutyl phenyl) pr0pane 2, 530, 353' particularly the aforeme 558 and 2,582,985.

Subdivision B 7 As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and 20 ntioned U. S. Patents Nos. 2,575,-

In light of the previous, excerpts from aforementioned U. S. Patent No. 2,575,558, the following examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

TABLE II H C-CC-- -0R [R],.-RiO-C0- 0Ri[R]-R10C-C-C H: H H: H: J) H, H: H H:

(in which the characters have their previous significance) Example -R1O- from HR1OBI R 'n 1: Remarks number B1 Hydroxy benzene CH 1 0,1,2 Phenol known as bis-phenol A. Low 1 polymeric mixture about as or more C where n=0, remainder largely where l n'=1, some where 'n=2. CH:

B2 ..do CH3 1 0, 1, 2 Phenol known as bis-phenol B. See note 0 regarding B1 above. I I (3H2 CH:

B3 Orthobutylphenol OH; 1 0, 1, 2 Even though 12 is preferably 0, yet the I usual reaction product might well con- C tain materials where 'n is 1, onto a l lesser degree 2. CH:

B4 Orthoamylphenol (EH; 1 0,1,2 Do.

, I CH:

B5 Orthooctylphenol CH: 1 0, 1,2 Do.

B6 Orthononylphenol (1H1 1 0, 1,2 Do.

..(i] 7 CH3 B7 Orthododecylphenol ([311: 1 0, 1, 2 D0.

. .(IJ CH3 B8 Metacresol CH; 1 0, 1, 2 See prior note. This phenol used as I initial material is known as bis-phenol C- C. For other suitable bis-phenols see I U. S. Patent 2,564,191. CH:

B9 .do $11; 1 0, 1, 2 Bee prior note.

CH: 6H:

B10 Dibuty1(ortho-pare) phenol. 15 1 0, l, 2 Do B11 Diamyl (ortho-para) phenol. g 1 0,1,2 D0.

TABLE II (continued) Example R from HR OE R- n n Remarks number 1312..-..- Dioctyl (ortho-parn) phenol. 101 1 0, 1, 2 See prior note.

B13 Dinonyl (ortho-para) phenol. g 1 0,1,2 Do.

B14 Diamyl (ortho-para) phenol. g 1 0,1,2 Do.

I CE;

Bl--- do H 1 0, 1, 2 Do.

CzHi

316...--. Hydroxy benzene (I) 1 0,1,2 D0.

B17 Diamyl phenol (ortho-pera). -S--S 1 0, 1, 2 Do.

B18 do S- 1 0, l, 2 Do.

B19 Dibutyl phenol (ortho-para). 1g 1g 1 0,1,2 D0.

B20 ..d0 H H 1 0, 1, 2 Do.

C C H H B21 Dinonylpheuol (ortho-para) 13 I3 1 0,1,2 Do.

B22 Hydroxy benzene (n) 1 0,1,2 D0

B23 dn Non 0 0,1,2 Do.

B24 Ortho-isopropyl phenol CH: 1 0,1,2 See prior note. As to preparation 014,4-

] isopropylidene bls-(z-isopropylphenol) C see U. S. Patent No. 2,482,748, dated Sept. 27, 1949, to Dietzler. CH;

B25 Para oct l he 1 CH SCH 1 0 1 2 See prior note. (As to preparation of the y p no rd 2 phenol sulfide see U. S Patent No. 2,488,134, dated Nov. 15, 1949, to Mikeska et 51.)

B26 H drox hen ene OH 1 01 2 See prior note. (As to preparation ofthe y y Z l a phenol sulfide see U. 8. Patent No.

EH: l 01H! Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

HO OH atoms.

Other samples include:

wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon See U. S. Patent No. 2,515,907.

Cs u s n in which the C5H11 groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

See U. S. Patent No. 2,285,563.

See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH II R ('3 R1 R:

wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

HaCP--CH; HaC- CH3 H3 H3 See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

Alkyl Alky] in which R5 is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U. S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH CH: CH: OH

in which R1 and R2 are alkyl groups, the sum of Whose carbon atoms equals 6 to about 20, and R and R2 each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 i It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH H H UCU JG H H R R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in' any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such at a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side: reactions may take place. For instance, 2 molesof amine may combine with one mole of .thealdehyde, or. only one mole of the amine may combine with the resin. molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As h-as been pointedout previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as aceta-ldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalystor basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presense of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE III M01. wt.

Ex- 11'" of resin ample R Positlon derived 7!, molecule number of R l'rom- (based on n+2) 1a Phenyl Para. Formal- 3. 5 992. 5

Tertiary butyl 3. 5 882. 5 3. 5 882. 5 3. 5 1, 025. 5 Tertiary amy do 3. 5 959. 5 Mixed secondary Ortho..- 3. 6 805. 5

and tertiary amyl.

Para. 3. 5 805. 5 3. 5 l, 036. 5 3. 5 l, 190. 5 3. 5 l, 267. 5 3. 5 1,344. 5 3. 5 1, 49s. 5 Tertiary butyl. 3. 5 945. 5

Tertiary amyl -do do.. 3. 5 1, 022. 5 Nonyl do do 3.5 1, 330.5 Tertiary butyl do Butyral- 3. 5 1,071. 5

dehyde. Tertiary amyl do o 3. 5 1,148.5 Nonyl do .do 3. 5 1, 456. 5 Tertiary butyl do-..-- Propion- 3. 5 1, 008. 5

aldehyde.

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4. 2 1, 430. 6 Tertiary butyl 4. 8 1, 094. 4 Tertiary amyl. 4. 8 1, 189. 6 4. s 1, 570. 4 1. 5 604. 1. 646. 0 1. 5 653. 0 1. 5 688. 0

PART 5 The expression cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or 'three additional carbon atoms completing the ring. All

the carbon atoms may be substituted. The nitrogen atom ofrthe ring involving two monovalent linkages may be substituted. Needless to say, these compounds include members in which the substituents also may have one or more nitrogen atoms, either in the form of amino nitrogen atoms or in the form of acylated nitrogen atoms.

These cyclic amidines are sometimes characterized as being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid, such as a low molal fatty acid, a high molal fatty acid, or comparable acids such as polycarboxy acids. Cyclic amidines obtained from oxidized wax acids are described in detail in co-pending Blair application, Serial No. 274,075, filed February 28, 1952. Instead of being derived from oxidized wax acids, the cyclic compounds herein employed may be obtained from any acid from acetic acid upward, and may be obtained from acids, such as benzoic, or acids in which there is a reoccurring ether linkage in the acyl radical. In essence then, with this difierence said aforementioned'co-pending Blair ap- 20 plication, Serial No. 274,075, describes compounds of the following structure:

where R is a member of the class consisting of hydrocarbon radicals having up to approximately 30 carbon atoms and includes hydroxylated hydrocarbon radicals and also hydrocarbon radicals in which the carbon atom chain is interrupted by oxygen; n is the numeral 2 to 3, D is a member of the class consisting of hydrogen and organic radicals containing less than 25 carbon atoms, composed of the elements from the group consisting of C, N, O and H, and B is a member of the group consisting of hydrogen and hydrocarbon radicals containing less than 7 carbon atoms, with the proviso that at least three occurrences of B are hydrogen.

The preparation of an imidazoline substituted in the two-position by lower aliphatic hydrocarbon radicals is described in the literature and is readily carried out by reaction between a monocarboxylic acid or ester or amide and a diamine or polyaminc, containing at least one primary amino group, and at least one secondary amino group or a' second primary amino group separated from the first primary amino group by two carbon atoms.

Examples of suitable polyamines which can be employed as reactants to form basic nitrogen-containing compounds of the present'invention include polyalkylene polyamines such as ethylene-diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and higher polyethylene polyamines, and also including 1,2-diamino propane, N-ethylcthylenediamine, NJJ-dibutyldiethylenetriamine, 1,2-diaminobutane, hydroxyethylethylenediamine, 1,2-propylenetriamine, and the like.

For details of the preparation of imidazolines substituted in the 2-position from amines of this type, see the following U. S. patents: U. S. No. 1,999,989, dated April 30, 1935, Max Bockmuhl et al.; U. S. No. 2,155,877, dated April 25, 1939, Edmund Waldmann et al.; and U. S. No. 2,155,878, dated April 25, 1939, Edmund Waldmann et a1. Also see Chem. Rev., 32, 47 (43).

Equally suitable for use in preparing compounds of my invention and for the preparation of tetrahydropyrimi dines substituted in the 2-position are the polyamincs containing at least one primary amino group and at least one secondary amino group, or another primary amino group separated from the first primary amino group by three carbon atoms. This reaction is generally carried out by heating the reactants to a temperature of 230 C. or higher, usually within the range of 250 C. to 300 C., at which temperatures water is evolved and ring closure is eiiected. For details of the preparation of tetrahydropyrimidines, see German Patent No. 700,371, dated December 18, 1940, to Edmund Waldmannand August Chwala; German Patent No. 701,322, dated January 14, 1941, to Karl Miescher, Ernst Erech and Willi Klarer; and U. S. Patent No. 2,194,419, dated March 19, 1940, to August Chwala.

Examples of amines suitable for this synthesis include 1,3-propylenediamine, trimethylenediamine, 1,3- diaminobutane, 2,4-diaminopentane, N-ethyl-trimethylenediamine, N-aminoethyltrimethylene diamine, aminopropyl stearylamine, tripropylenetetramine, tetrapropylenepentamine, high boiling polyamines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyarnines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

Similarly, the same class of materials are included as initial reactants in co-pending. Smith application, Serial No. 281,645, filed April 10, 1952. Said application in essence states that the cyclic compounds employed may be derived from either polyamines in which the nitrogen atoms are separated by an ethylene radical or by a trimethylene radical. Reference to a propylene radical means a methyl substituted ethylene radical, i. e., having only 2 carbon atoms between nitrogen atoms. From a practical standpoint, as will be explained hereinafter, the polyethylene imidazolines are most readily available and most economical for use. Thus, broadly speaking, using the same terminology as said Smith application, Serial No. 281,645, the present invention is concerned with a condensation reaction, in which one class of react-ants are substituted ring compounds consisting of in which R is a divalent alkylene radical selected from the class consisting of and in which D represents a divalent, non-amino, organic radical containing less than 25 carbon atoms, composed of elements from the group consisting of C, H, O, and N; Y represents a divalent, organic radical containing less than 25 carbon atoms, composed of elements from the group consisting of C, H, O, and N, and containing at least one amino group, and R is a member of the class consisting of hydrogen, aliphatic hydrocarbon radicals, hydroxylated aliphatic hydrocarbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cyloaliphatic hydrocarbon radicals; R is a member of the class consisting of hydrogen, aliphatic radicals and cycloaliphatic radicals, With the proviso that in the occurrence of the radicals R and R there be present at least one group of 8 to 32 uninterrupted carbon atoms. In the present instance, however, there is no limitation in regard to the radicals R and R".

What has been said previously in regard to the two above co-pending applications as far as substituted imidazolines are concerned is substantially the same as appears in Blair and Gross Reissue Patent No. 23,227, reissued May 9, 1950, and Monson Patent No. 2,589,198 dated April 11, 1952.

As to the six-membered ring compounds generally referred to as substituted pyrimidines, and more particularly, as substituted tetra-hydropyrimidines, see U. S. Patent No. 2,534,828, dated December 19, 1950, to Mitchell et al. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of the fivemembered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned U. S. Patent No. 2,534,828.

For the purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations: (a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two-ring membered radicals present instead of one ring-membered radical and may or may not have present a tertiary amine radical or a hydroxyl radical, such as a hydroxy alkyl radical. A largenumber of compounds have been described in the literature meeting the above specifications, of which quite a few CiHs-O NGH2 C2H4.NH. CwHzr 1-N-decy1aminoethy1,Z-ethylimidazoline N-CH2 0 H3. 0

NO H2 CzH4.NH. C2H4.NH. CieHss 2-methyl,1-hexadecylaminoethylaminoethylimidazoline /NO H2 H. C\

1TTCH2 O3Hu.NH. CrzHrtt 1-dodecylaminopropylimidazoline /N C H2 H. O

C2H4.NH. CzH4O CH.C17H! I 1- stearoyloxyethyl) aminoethylimidazoline' /NOH2 H. C

CZHLNH. C2H4NHO C C11H2l 1-stearamidoethylaminoethylimidazoline NO H 1- (N-dodecyl) -acetamidoethylaminoethylimidazoline C 7Ha5C N -CH-CH3 2-heptadecyl,4,5-dimethy1imidazo1ine N CH2 I;TCH O BHILN H 612E 1-dodecylaminohexylimidazoline N G H2 C H12.NH.CzH .O 0 91135 v l-stearoyloxyethylaminohexylimidazoline 2-heptadocyl,l methylaminoethyltetrahydropyrimidine C12H25-C/ CH2 14 n-o. CH2 lzHrNH C 2H4N 4-methyl,2-dodecyl,l-methylaminoethylaminocthyl to trahydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted irnidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula:

Such compounds can be derived, of course, from triethylenetetrarnine, tetraethylenepentamine, pentaethylenehexamine, and higher homologues. The substituents may vary depending on the source of the hydrocarbon radical, such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or the like. The group introduced may or may not contain a hydroxyl radical as in the case of hydroxyacetic acid, acetic acid, ricinoleic acid, oleic acid, etc.

One advantage of a two-ring compound resides in the fact that primary amino groups which constitute the terminal radicals of the parent polyamine, whether a polyethylene amine or polypropylene amine, are converted so as to eliminate the presence of such primary amino radicals. Thus, the two-membered ring compound meets the previous specification in regard to the nitrogen-containing radicals.

Another procedure to form a two-membered ring compound is to use a dibasic acid. Suitable compounds are described, for example, in aforementioned U. S. Patent No. 2,194,419, dated March 19, 1940, to Chwala.

As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyamines in which the terminal groups are unsymmetrically alkylated. Initial polyamines of this type are illustrated by the following formula:

in which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a small whole number greater than unity such as 2, 3 or 4. Substituted imidazolines can only be formed from that part of the polyarnine which has a primary amino group present. There is no objection to the presence of a tertiary amino radical as previously pointed out. Such derivatives, provided there is more than one secondary amino radical present in the ring compound, may be reacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as to convert one or more amino nitrogen radicals into the corresponding hydroxy alkyl radical, provided, however, that there is still a residue secondary amine group. For instance, in the preceding formula if n represents 4 it means the ring compound would have two secondary nitrogen radicals and could be treated with a single mole of an alkylene oxide and still provide a satisfactory reactant for the herein described condensation reaction.

Ring compounds, such as substituted imidazolines, may be reacted with a substantial amount of alkylene oxide as noted in the preceding paragraph and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkylating agent such as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic acid, an alkyl bromide, etc.

As to oxyalkylated imidazolines and a variety of suitable high molecular weight carboxy acids which may be the source of a substituent radical, see U. S. Patent No. 2,468,180, dated April 26, 1949, to De Groote and Keiser.

Other suitable means may be employed to eliminate a terminal primary amino radical. If there is additionally a basic secondary amino radical present then the primary amino radical can be subjected to acylation notwithstanding the fact that the surviving amino group has no significant basicity. As a rule acylation takes place at the terminal primary amino group rather than at the secondary amino group, thus one can employ a compound such as N-CH 2-heptadocyl,1-diethyleuediaininoimidazoline and subject it to acylation so as to obtain, for example,

acetylated 2-heptadecyl,l diethylenediaminoimidazoline of the following structure:

propylene oxide, glycide, etc., to yield a perfectly satis- 25 factory reactant for the herein described condensation procedure. This can be illustrated in the following manher by a compound such as 2-heptadecyl,l-aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of Z-heptadecyl,1-amino-ethylimidazoline, which can be illustrated by the following formula:

NCHz

C11Hss-0 6) Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, Z-heptadecyl,l-amino-ethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. if reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amino group. if ethylene imine is employed, the net result is simply to convert Z-heptadecyl,l-aminoethylimidazoline into Z-heptadecyl,1-diethylene-diaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group between nitrogen atoms.

A more satisfactory reactant is to employ one obtained by the reaction of a epichlorohydrin on a secondary alkyl amine, such as the following compound:

If a mole of Z-heptadecyl,l-aminoethylimidazoline is reacted with a mole of the compound just described, to wit,

the resultant compound has a basic secondary amino group and a basic tertiary amino group. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Groll.

For purpose of convenience, what has been said by direct reference is largely by way of illustration in which there is present a sizable hydrophobe group, for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups, etc. etc.

As has been pointed out, one can obtain all these comparable derivatives from low molal acids, such as acetic, propionic, butyric, valeric, etc. Similarly, one can employ hydroxy acids such as giycolid acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe elfect as, for example, acids prepared by the oxyethylation of a low molal alcohol,

26 such as methyl, ethyl, propyl, or the like, to produce compounds of the formula.

in which R is a low molal group, such as methyl, ethyl or propyl, and n is a whole number varying from one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloracetic, followed by saponification so as to yield compounds of the type R(OCH2CH2)nOCI-I2COOH in which n has its prior significance. Another procedure is to convert the compound into a halide ether such as in R(OCH2CHz)nCl in which n has its prior significance, and then react such halide ether with sodium cyanide so as to give the corresponding nitrile R(OCH3CH3)7LCN, which can be converted into the corresponding acid, of the following composition R(OCH2CH2)1LCOOH. Such acids can also be used to produce acyl derivatives of the kind previously described in which acetic acid is used as an acylating agent.

What has been said above is intended to emphasize the fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and have a minimum hydrophobe property.

Examples of decreased hydrophobe character are exemplified by 2-methylimidazoline, Z-propylimidazoline, and Z-butylimidazoline, of the following structures:

H-CHz PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general Way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-aminealdehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of scribed in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyph'ase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethylenegiycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, para-formaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if thereis to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxy-acetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In

28 fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this, (c) is an elfort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then'the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On .the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene; Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned -U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred.

Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threephase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difiiculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C, or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays Within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. in some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. in other cases we have used a slight excess of nitrogen compound, and, again, have not found any particular advantage in so do ing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the endproduct showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n' which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 35 C. and 612 grams of 2-oleylimidazoline, previously shown in a structural formula as ring compound (3), were added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 /2 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table IV following there are a large number of added examples illustrating the same procedure. in each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table IV.

TABLE IV Amt. of Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used amine, formaldehyde Solvent used tiou tlon distill N0. used grs. grams soln. and and amt. temp., time teIHIL,

amt. 0. (hrs.) C.

612 37%, 162 g Xylene, 600 g 20-25 30 148 306 37%, 81 g Xylene, 450 gut. 24 145 306 Xylene, 600 g 28 150 281 30%, 100 g Xylene, 400 28 148 281 .do... Xylene, 450 g 30 148 281 37%, 81 g Xylene, 600 g 26 146 394 .dO Xylene, 400 g. 23-28 26 147 Xylene, 450 gm. 22-26 26 146 Xylene, 600 g 21-25 38 i 150 Xylene, 450 g -24 36 149 Xylene, 500 21-22 24 142 Xylene, 650 g 20-21 26 145 Xylene, 425 22-28 28 146 Xylene, 450 23-30 27 150 Xylene, 550 20-24 29 147 Xylene, 440 2... 20-21 30 148 Xylene, 480 g 21-26 32 146 Xylene, 600 21-23 26 147 Xylene, 500 g 21-32 29 150 do 21-30 32 150 Xylene, 550 g 21-23 37 150 Xylene, 440 g 20-22 30 150 do Xylene, 600 g 20-25 36 149 30%, 50 55.... Xylene, 400 g 20-24 32 152 The amine numbers referred to are the ring compounds identified previously by number in Part 5.

PART 7 The products obtained as herein described by reactions involving amine condensation and diglycidyl ethers It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may require a pressure vessel as in the case of ethylene oxide, it is convenient to use the same reaction vessel in both instances. In other words, the 2 moles of the amine-modified phenol-aldehyde resin condensate would be reacted with a polyepoxide and then subsequently with a monoepoxide. in any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture go as described in a number of patents, as for example, U. S.

Patent No. 2,499,365.

Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin K5 condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a non- ()0 basic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium 7 methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i.e., one that is not oxyalkylanon-susceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1C The product was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained from resin 5a; resin 5a was obtained from tertiary amylphenol and formaldehyde. Condensate 2b employed as reactants resin 5a and Amine 3, referred to in Table IV preceding, and more specifically the compound 2-oleylimidazoline. The amount of resin employed was 480 grams, the amount of 2-oleylimidazoline employed was 306 grams, the amount of 37% formaldehyde employed Was 81 grams, and the amount of solvent employed was 450 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of the diepoxide.

In any event, grams of the condensate dissolved in approximately an equal weight of xylene were stirred and heated to slightly above the boiling point of water. 17 grams of the diepoxide previously identified as 3A and dissolved in an equal weight of xylene were added dropwise. The initial addition of the xylene solution carried the temperature to slightly above the boiling point of water. The remainder of the diepoxide was added during approximately a 50 minute period. During this TABLE VIII period of time the temperature rose to about 122 C. Probable The temperature was allowed to rise slightly and the Resin con- Proba-ble Amtof Amt. of number of product refluxed at about 130 C. using a phase-separatf gzg 1 m? 3 2 515 35 25 ing trap. A small amount of xylene was removed by 5 product cule means of the phase-separating trap so the temperature gradually rose to 150 C. and the product was refluxed 3,740 3,740 1,870 11 at this temperature for about 6 hours. After this period 5% 818 2 828 i 35? of time the xylene which had been removed during the 41) 811 41090 4; 100 2: 055 11 reflux period was returned to the mixture. A small 23:: ig z: $228 2 932 5 288 amount of material was withdrawn and the xylene evap- 7D 135 2, 940 a: 940 11970 u I I orated on a hot plate in order to examine the physical 38:: igg ggig 3'82? i'ggg i; properties. The material was a dark red viscous semi- 10D b 3,170 3,175 1,590 12 solid. It was insoluble in water, and it was insoluble in 5% gluconic acid; 1t was soluble in xylene and par- 15 At this point it may be desirable to direct attention tlclllally In mlxtufe 9 30% Xylene and me h to two facts, the first being that we are aware that other However, If the materlal W dlSSOlVed xyg n diepoxides free from an aromatic radical as, for example, solvent 'and then shaken wlth 5% glucomc ac1d 1t showed e oxides derived from ethylene glycol, glycerine, or the a definite tendency to dlsperse, suspend, or form a sol, lik h as th f ll i and particularly in a xylene-methanol mixed solvent as 20 V H H H H H H n previously descnbed, Wlth or without the further addl- Ho--o0o-o-o0o-ou tion of a little acetone. H g H The procedure employed of course is simple in light H H H H H of what has been said previously and in eifect is a pro- HC- -()OC QOC- CH cedure similar to that employed in the use of glycide H H or methylglycide as oxyalkylating agents. See, for example, Part 1 of U. S. Patent No. 2,602,062 dated July 1, may be employed to replace the diepoxides herein de- 1952, to De Groote. scribed. However, such derivatives are not included as Various examples obtained in substantially the same Part of th In tant lnv ntlon. manner are enumerated in the following tables: At times we have found a tendency for an insoluble TABLE V Oon- Time Ex. den- Amt, Di- Amt., Xylene, Molar of reac- Max. No. sate grs. epoxide grs. grs. ratio tion, temp., Color and physical state used used hrs. C.

160 3A 17 177 2:1 8 150 Dark solid mass. 155 3A 17 172 2:1 7 155 Do. 169 3.4 17 186 2:1 3 158 D0. 177 3A 17 194 2:1 8 155 Do. 173 3A 17 190 2:1 8 150 Do. 211 3A 17 228 2:1 8 152 Do. 170 3A 17 187 2:1 8 158 Do. 124 3A 17 141 2:1 5 100 Do. 125 3A 17 142 2:1 6 152 Do. 131 3A 17 148 2:1 6 158 Do.

TABLE VI Oon- Time Ex. den- Amt, Di- Amt, Xylene, Molar of reac- Max. No. sate grs. epoxide grs. grs. ratio tion, temp., Color and physical state used used hrs. C.

160 B1 27. 5 188 2: 1 8 155 Dark solid mass. 155 B1 27. 5 133 2:1 8 150 Do. 169 B1 27. 5 197 2:1 8 162 Do. 177 B1 27. 5 205 2:1 8 158 Do. 173 B1 27. 5 200 2: 1 s 165 Do. 211 B1 27. 5 239 2: 1 s 150 Do. 170 B1 27. 5 198 2: 1 s 151 Do. 124 B1 27.5 152 2:1 7 164 D0. 125 B1 27.5 153 2:1 7 158 D0. 131 B1 27.5 159 2:1 7 100 Do.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diep'oxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to re duce the amount of catalyst used, or reduce the term perature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance to instead of 75 The reason for this fact may reside in the possibility 35 that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CHz(Resin)CHz(Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepox-ide, would be indicated thus:

[(Amine) CH2 (Resin) CHz(Amine)] /D.G.E. [(Amine) CH2( Resin) CHz(Amine)] in which D. G. E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity \of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CH1 (Amine)] [D G .E

[(Amine) CHg(A1'nine)] [(Resin) OH2(Resin)] [D G .E

[(Rcsin) CH2 (Resin)] [(Amine) OHz(Amine)] [D.G.E.]

[(Resin)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc, may be/employ'ed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of de mulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000 or 1 to 30,000, or even 1 to 40,000 or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and Water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

In practicing the present process, the treating or demulsifying agent is used in the conventional Way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures 'of demulsifying, including batch, continuous, and down-the-hole 'demulsification, the process essentially iii-- An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%; a

A sodium salt of toil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 57%.

The above proportions are all Weight percents,

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier,-said demulsifier being obtained by first (A) condensing (a) an oxyalkylatiorn susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methyl'ol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said. condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and withthe pl'lOVlSO that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting saidresin condensate with a phenolic polyepoxide free from reactive functional groups other than epoxy and hydroxyl groups and cogenerically associated compounds formed in the preparation of said p-olyepoxides; said ep'ox-ides being monomers and low mclal polymers not exceeding the tetramers; said'polyepoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of kctone residues formed by the elimination 37 radical the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical and the divalent disulfide radical -S--S--; said phenolic portion of the diepo-xides being obtained from a phenol of the structure III RI! I in which R, R, and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 mole-s of the resin condensate to 1 mole of the phenolic polyepoxide.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) cyclic amidines selected from the class consisting of substituted imidaz'olines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate Water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting phenolic epoxides being principally polyepoxides, including phenolic diepoxides; said epoxides being free from reactive functional groups other than epoxy and hydroxyl groups, and including additionally cogenerically associated compounds formed in the preparation of said polyepoxides'and diepoxides, said epo-Xides being monomers and low molal polymers not exceeding the tetramer; said eproxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues 38 obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent radical -CH2SCH2, and the divalent disulfide radical --SS; said phenolic portion of the diepoxide being obtained from a phenol of the structure III in which R, R, and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and resultants of reaction. 3. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylation-susceptiblc, fusible, non-oxygenated organic solvent-soluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R isan aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consist of substituted imidazolines and sub stituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oXyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramers; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues 39 obtained by the elimination of the aldehydic' oxygen atom, the divalent radical the structure in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obtained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at last one basic secondary amino radical and characteriZed by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepo-xide free from reactive functional groups other than epoxy and hydroxyl groups, and cogenerically associated compounds formedin the preparation of said diepoxides; said epoxides being so lected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone' residues formed by the elimination of the ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atomfthe divalent radical H H C C H H the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S', the divalent radical CH2SCH2 and the divalent disulfide radical -SS; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the ratio of reactant (A) to reactant (B) being at least sufi'icient so there is available at least one active hydrogen in (A) for each oxirane ring in the diepoxide reactant (B); with the further proviso that said reactive compounds (a) and (B) the members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) be conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier, said demulsifier being obv tained by first (A) condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction betweenfa difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms'and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class-consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B). reacting a phenolic diepoxide free from. 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY FIRST (A) CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 